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WO2025132849A1 - Précurseur de matériau de batterie à base d'hydroxydes métalliques mixtes produit à partir de charges de recyclage de batterie - Google Patents

Précurseur de matériau de batterie à base d'hydroxydes métalliques mixtes produit à partir de charges de recyclage de batterie Download PDF

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WO2025132849A1
WO2025132849A1 PCT/EP2024/087489 EP2024087489W WO2025132849A1 WO 2025132849 A1 WO2025132849 A1 WO 2025132849A1 EP 2024087489 W EP2024087489 W EP 2024087489W WO 2025132849 A1 WO2025132849 A1 WO 2025132849A1
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cations
solution
solid
liquid separation
cstr
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Inventor
Vincent Smith
Bernard Muller
Tomi Oja
Joop Enno FRERICHS
Kathrin Michel
Rafael Benjamin BERK
Regina Vogelsang
Kerstin Schierle-Arndt
Wolfram WILK
Maximilian RANG
Anne-Marie Caroline ZIESCHANG
Wolfgang Rohde
Fabian Seeler
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/30—Oximes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0476—Separation of nickel from cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy

Definitions

  • the present disclosure relates to a continuous process and a production plant for producing a mixed metal hydroxide battery material precursor from battery recycling feeds comprising nickel, cobalt, manganese, and lithium cations.
  • Lithium ion battery materials are complex mixtures of various elements and compounds. For example, many lithium ion battery materials contain valuable metals such as lithium, aluminum, copper, nickel, cobalt, and/or manganese. It may be desirable to recover various elements and compounds from lithium ion battery materials. For example, it may be advantageous to recover lithium, aluminum, copper, nickel, cobalt, and/or manganese. Accordingly, there is a need for devices and processes for recycling lithium ion battery materials.
  • WO 20231054621 A1 discloses a method for recovering valuable metals from waste lithium ion batteries comprising a dissolution step for dissolving an active material powder obtained by pre-treating the waste lithium-ion batteries in a mineral acid to obtain an acid solution; and a solvent extraction step for separating manganese, cobalt, and nickel, among metals contained in the active material powder, from the acid solution through solvent extraction to obtain a first lithium salt aqueous solution as a residual liquid of the solvent extraction.
  • WO 2020 / 124130 A1 discloses a method for the recovery of metals from a feed stream containing one or more value metals and lithium.
  • the method comprises subjecting the feed stream to a sulfuric acid leach to form a slurry comprising a pregnant leach solution of soluble metal salts and a solid residue; separating the pregnant leach solution and the solid residue; subjecting the pregnant leach solution to one or more separate solvent extraction steps, wherein each solvent extraction step recovers one or more value metals from the pregnant leach solution, the remaining pregnant leach solution comprising lithium; and recovery of lithium from the pregnant leach solution.
  • CN 111 455 171 A discloses a method of extracting valuable metal from a seabed polymetallic nodule resource, in particular to a method of using the seabed polymetallic nodule resource as a raw material to produce copper sulfate, manganese sulfate, titanium dioxide, a lithium battery ternary cathode material precursor and a titanium-doped cathode material through a whole wet method process.
  • the seabed polymetallic nodule resource is subjected to sulfuric acid high-pressure leaching operation, copper, nickel, cobalt and manganese in leachate are subjected to chemical precipitation, extraction separation and purification, a nickel cobalt manganese sulfate solution which is obtained through combined extraction is subjected to chemical precipitation to produce the lithium battery ternary cathode material precursor, and the precursor is subjected to lithiation, titanium doping and calcination operation, so that the titanium-doped ternary cathode material is obtained.
  • the hydrometallurgical process of battery recycling to obtain battery grade Ni, Mn and Co sulfates includes various recovery and purification steps, like solvent extraction. Combining this hydrometallurgical process with the precipitation of a cathode material precursor, the first step in the production of cathode active materials for lithium-ion batteries, would offer the opportunity to skip purification steps and save costs.
  • a prerequisite to precipitate the precursor is a sufficiently high metal concentration of about 80 g/l nickel.
  • bases like NaOH or Na 2 CO3 are commonly used for pH adjustment in all process steps after acid leaching, leading to Na 2 S0 4 formation. This leads to high Na load and prohibits achieving sufficient nickel concentration by evaporation of a recycling feed (e.g., before Ni solvent extraction), as a NiNa(SO 4 ) 2 double salt is formed and the minimum nickel concentration cannot be achieved.
  • the process of the present disclosure improves the prior art hydrometallurgical recycling process either by replacing NaOH by alternative bases like CaO, Ca(OH) 2 or MHP (commercial mixed metal hydroxide precipitate from mining) in some of the recycling process steps.
  • the present disclosure provides a continuous process for producing a mixed metal battery material precursor.
  • the process involves providing an aqueous acidic solution comprising nickel, cobalt, manganese, and lithium cations, which has been obtained by acid leaching of a lithium-ion battery material, removing manganese cations and impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, or Si present in the solution from the solution by precipitation, followed by solvent extraction of manganese and impurity cations, solvent extraction of cobalt cations, adding CoSO 4 and MnSO 4 to the aqueous solution depleted of cobalt cations, adding sodium hydroxide and ammonia to the solution and precipitating and recovering a precursor of an cathode active material for lithium-ion batteries.
  • the present disclosure also provides a production plant suitable for performing the continuous process of the present disclosure. Brief description of the drawings
  • Fig. 1 is a schematic diagram of an exemplary production plant of the present disclosure.
  • the present disclosure provides a continuous process for producing a mixed metal battery material precursor from an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.
  • the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations has been obtained by leaching lithium ion battery materials with sulfuric acid.
  • suitable lithium ion battery materials for preparing the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations include black mass, cathode active materials, and mixed metal hydroxides (MHP).
  • the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations may additionally contain cations of other metals like copper, manganese, iron, aluminum, magnesium, calcium, and/or titanium; as well as anions like fluoride and/or phosphate.
  • the continuous process of the present disclosure comprises the steps of a) optionally, adjusting the pH of the solution to a value in the range of from 1 .5 to 2.5 and recovering copper from the solution by solvent extraction or by precipitation of copper sulfide, followed by solid/liquid separation, b) adjusting the pH of the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations to be in the range of from 3.0 to 4.0 by addition of calcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, barium carbonate, and/or MHP, and subsequently precipitating impurity cations of the group consisting of Al and Fe cations and impurity anions comprising P, F, or Si present in the solution from the solution, c) removing solids from the mixture obtained in step b), d) adjusting the pH of the acidic aqueous solution obtained in step c) to be in the range of from 4.5 to 5.0 by addition of calcium oxide, calcium hydroxide,
  • the process further comprises the steps of l) adjusting the pH of the aqueous solution obtained in step k) to be in the range of from 8 to 12, e.g., from 8 to 10, for instance, from 8 to 9; and subsequently removing lithium cations from the solution by solvent extraction to obtain an aqueous solution depleted of lithium cations and an organic solvent comprising lithium cations; and scrubbing and stripping the organic solvent comprising lithium cations with sulfuric acid to obtain an acidic aqueous solution comprising lithium cations.
  • copper is recovered by a first solvent extraction from the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.
  • Solvent extraction is a useful method for separating and purifying metal ions from an aqueous solution or leachate. This can be difficult when purifying metal ions present in a hydrated form in an aqueous solution, since it is difficult to move the ions to an organic solvent layer having a low polarity. In order to move hydrated metal ions to the organic phase, the metal ions should be in a form of an uncharged complex and the metal ions should be able to remove water molecules from the hydrated complex.
  • a solvent extracting agent allows the metal ions to form a non-charged complex and remove water molecules.
  • the extraction efficiency depends on, e.g., the type of solvent extracting agent, the equilibrium pH, and the metal ions in the aqueous solution.
  • the extraction efficiency may also be affected by, e.g., the concentration of the solvent extracting agent, the ratio of the solvent extracting agent to the aqueous solution, and the composition and concentration of the stripping solution.
  • the solvent extracting agent is LIX984N, a 1 :1 mixture of 5-nonyl salicylaldoxime and 2-hydroxy-5- nonyl acetophenone.
  • the first solvent extraction comprises
  • the first solvent extraction is a two-step process (or even a three-step process if impurities need to be scrubbed before the stripping).
  • the optional step of scrubbing (step 2) if necessary, is carried out in-between the extraction of the target species into the organic phase (step 1 ) and the stripping (step 3).
  • a solvent extracting agent (a non-polar weak acid) is dissolved in an organic liquid (diluent), such as kerosene. This mixture forms the extracting agent solution. This solution is brought into contact/mixed with the acidic aqueous solution, from which the extracting agent selectively extracts copper cations.
  • impurities are removed from the organic phase (the extracting agent solution) by scrubbing.
  • the extracting agent solution which now comprises copper cations
  • an acid solution strong acid
  • H + strong acid
  • the copper cations transfer into the acidic aqueous solution.
  • This solution is then called loaded stripping solution.
  • stripping The process of transferring the copper cations back into an aqueous phase.
  • copper is recovered by precipitation followed by solid/liquid separation.
  • the copper ions are removed by precipitation of copper sulfide.
  • sulfide, hydrogen sulfide, or thiosulfate ions are added to the solution.
  • Na 2 SO3 is added to the solution to precipitate copper sulfide.
  • the precipitate is separated from the aqueous solution depleted of copper cations by solid/liquid separation, for instance, by filtration.
  • the acidic aqueous solution depleted of Cu obtained after the first solvent extraction, or after precipitation of copper sulfide, followed by solid/liquid separation, is further processed in step b).
  • step b) of the process of the present disclosure impurities are precipitated from the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.
  • the precipitation involves the addition of calcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, barium carbonate, and/or MHP.
  • MHP mixed hydroxide precipitate
  • MHP means a mixture of metal hydroxides, hydroxycarbonates, and/or carbonates comprising nickel hydroxide, cobalt hydroxide and other metals, e.g., manganese.
  • the MHP is obtained by precipitating metal hydroxides from a metal salt solution.
  • MHP typically comprises from 0 to 2 wt.% Li, from 10 to 50 wt.% Ni, from 0.1 to 20 wt.% Co, from 0.01 to 15 wt.% Mn.
  • Moisture content generally is in the range of from 20 to 60 wt.%, relative to the total weight of MHP.
  • a typical range for D(50) is from 1 to 150 pm.
  • the MHP is an intermediate nickel product produced from laterite nickel ore, which contains both nickel and a small percentage of cobalt. MHP is typically produced using a high-pressure acid leaching (HPAL) process.
  • HPAL high-pressure acid leaching
  • the mixed hydroxide precipitate (MHP) mostly consists of nickel hydroxide, but also contains valuable cobalt hydroxides and various other impurities, the main one being manganese. Ni content typically is 34-55 wt.%, Co content typically 1- 4.5 wt.%.
  • calcium oxide, calcium hydroxide, and/or calcium carbonate are added to generate a precipitate.
  • barium oxide, barium hydroxide, and/or barium carbonate are added to generate a precipitate.
  • MHP is added to generate a precipitate.
  • the impurities comprise one or more selected from iron, aluminum, magnesium, calcium, titanium, manganese, residual copper, fluoride, and phosphate.
  • the precipitation involves the addition of calcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, barium carbonate, and/or MHP to the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations, thereby adjusting the pH value of the solution to a value in the range of from 3.0 to 4.0.
  • air is injected into the solution to oxidize any Fe(ll) present to Fe(lll).
  • solid-liquid separation e.g., filtration.
  • calcium oxide, calcium hydroxide, and/or calcium carbonate are added to generate a precipitate.
  • barium oxide, barium hydroxide, and/or barium carbonate are added to generate a precipitate.
  • MHP is added to generate a precipitate.
  • the mother liquor is further processed in a second precipitation step d).
  • the precipitation involves the addition of calcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, barium carbonate and/or MHP to the mother liquor obtained in step c), thereby adjusting the pH value of the solution to a value in the range of from 4.5 to 5.0.
  • Iron, aluminum, magnesium, titanium, and copper precipitate from the solution as hydroxides and/or oxidehydroxides and/or carbonates, fluorides and/or phosphates, and are removed from the mother liquor in a subsequent step e) by solid-liquid separation, e.g., filtration.
  • some manganese also is precipitated as manganese carbonate.
  • the precipitate obtained in step e) may contain significant amounts of value metals, in particular, nickel, it can be recycled into a leaching step and used for generating an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.
  • value metals in particular, nickel
  • calcium oxide, calcium hydroxide, and/or calcium carbonate are added to generate a precipitate.
  • barium oxide, barium hydroxide, and/or barium carbonate are added to generate a precipitate.
  • MHP is added to generate a precipitate.
  • steps b) through e) maximizes precipitation of Al, Fe, F and thus the removal of impurities from the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations, and it minimizes co-precipitation of value metals, and thus minimizes losses of nickel, cobalt, manganese, and lithium.
  • the process further comprises f) adjusting the pH of the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations to be in the range of from 2 to 4 by addition of calcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, barium carbonate, and/or MHP, and subsequently removing manganese cations and any impurity cations of the group consisting of Ca, Cu, Zn, and Cd present in the solution from the solution by solvent extraction to obtain an aqueous solution depleted of manganese cations and impurity cations and an organic solvent comprising manganese cations and impurity cations, and scrubbing and stripping the organic solvent comprising manganese cations and impurity cations with sulfuric acid to obtain an acidic aqueous solution comprising manganese cations and impurity cations.
  • calcium oxide, calcium hydroxide, and/or calcium carbonate are added to adjust the pH.
  • barium oxide, barium hydroxide, and/or barium carbonate are added to adjust the pH.
  • MHP is added to adjust the pH.
  • Solvent extraction is performed in step f) using an organic solvent suitable for extracting manganese cations from an aqueous solution.
  • suitable organic solvents include bis(2-ethylhexyl)phosphate (D2EHPA).
  • the solvent used in step f) is a solution of 40 vol% bis(2- ethylhexyljphosphate (D2EHPA) in dearomatized hydrocarbon fluid (EscaidTM 110).
  • the process further comprises g) adjusting the pH of the acidic aqueous solution depleted of manganese cations and impurity cations obtained in step f) to be in the range of from 3 to 6; and subsequently removing cobalt cations from the solution by solvent extraction to obtain an aqueous solution depleted of cobalt cations and an organic solvent comprising cobalt cations, and scrubbing and stripping the organic solvent comprising cobalt cations with sulfuric acid to obtain an acidic aqueous solution comprising cobalt cations.
  • the pH value is adjusted by addition of calcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, barium carbonate, and/or MHP.
  • calcium oxide, calcium hydroxide, and/or calcium carbonate are added to adjust the pH.
  • barium oxide, barium hydroxide, and/or barium carbonate are added to adjust the pH.
  • MHP is added to adjust the pH.
  • Solvent extraction is performed in step g) using an organic solvent suitable for extracting cobalt cations from an aqueous solution.
  • suitable organic solvents include phosphinic acid derivatives, e.g., bis-(2,4,4-trimethyl- pentyl) phosphinic acid (Cyanex® 272).
  • the solvent used in step d) is a solution of 20 vol% bis-(2,4,4-trimethylpentyl) phosphinic acid (Cyanex® 272) in dearomatized hydrocarbon fluid (EscaidTM 110) containing 1 g/L butylhydroxytoluene (BHT).
  • the process further comprises h) removing water from the aqueous solution depleted of cobalt cations obtained in step g) to obtain an aqueous solution having a nickel concentration of at least 80 g/l.
  • the process further comprises i) adding cobalt sulfate and manganese sulfate to the solution obtained in step h) to obtain a solution comprising nickel, cobalt, and manganese in a predetermined molar ratio.
  • the molar ratio of Ni:Co:Mn is 0.91 :0.045:0.045.
  • the base is selected from alkali metal hydroxides and/or carbonates.
  • hydroxides of sodium, potassium and/or lithium are used as base.
  • sodium hydroxide is used as base.
  • potassium hydroxide is used as base.
  • lithium hydroxide is used as base.
  • a combination of alkali hydroxides is used as base.
  • the hydroxide concentration in the solution is in the range of from 0.1 to 12 mol/l, for instance, from 6 to 10 mol/l.
  • the complexing agent is ammonia and/or an organic acid or its alkali or ammonium salts, wherein said organic acid bears at least two functional groups per molecule and at least one of the functional groups is a carboxylate group.
  • suitable organic acids bearing two identical functional groups are adipic acid, oxalic acid, succinic acid and glutaric acid.
  • An example of organic acids bearing three identical functional groups is citric acid.
  • the organic acid is selected from malic acid, tartaric acid, citric acid, and glycine.
  • ammonia is used as complexing agent.
  • the concentration of complexing agent(s) in the solution is in the range of from 1 to 30% by weight.
  • the complexing agent is ammonia
  • its concentration preferably is in the range of from 10 to 30% by weight.
  • the concentration of said complexing agent in the solution preferably is in the range of from 0.2 to 10% by weight.
  • the process further comprises k) performing a solid/liquid separation of the mixture obtained in step j) to obtain a solid mixed metal battery material precursor and a mother liquor.
  • the mixed metal battery material precursors are (oxy)hydroxides or oxides comprising nickel and at least one transition metal selected from Co and Mn and optionally, at least one further element selected from Ti, Zr, Ca, Si, Mo, W, Al, Mg, Nb, and Ta.
  • the mixed metal battery material precursors of the present disclosure have an average particle diameter (D50) in the range of from 3 to 20 pm, e.g., from 5 to 15 pm, for instance, from 6 to 12 pm, determined by dynamic light scattering.
  • D50 average particle diameter
  • the mixed metal battery material precursors are comprised of secondary particles comprising asymmetric plate-like shaped primary particles that have a thickness of 20 to 200 nm and a length of 50 to 500 nm.
  • the primary particles are essentially radially aligned.
  • the portion of radially aligned primary particles may be determined, e.g., by SEM (Scanning Electron Microscopy) of a cross-section of at least arbitrarily selected 5 secondary particles. “Essentially radially alignment” does not require a perfect radial orientation but includes that in an SEM analysis, a deviation to a perfectly radial orientation is at most 5 degrees.
  • the process further comprises I) adjusting the pH of the aqueous solution obtained in step k) to be in the range of from 8 to 12, e.g., from 8 to 10, for instance, from 8 to 9; and subsequently removing lithium cations from the solution by solvent extraction to obtain an aqueous solution depleted of lithium cations and an organic solvent comprising lithium cations; and scrubbing and stripping the organic solvent comprising lithium cations with sulfuric acid to obtain an acidic aqueous solution comprising lithium cations.
  • Solvent extraction is performed in step I) using an organic solvent suitable for extracting lithium cations from an aqueous solution.
  • organic solvents include synergistic extractant mixtures comprising a betadiketone and a neutral extractant, e.g. an organic phosphate, as disclosed in J Chem Technol Biotechnol 2016; 91 : 2549-2562 (table 3); Hydrometallurgy 154 (2015) 33-39; and Hydrometallurgy 175 (2016) 35-42.
  • Further examples of suitable organic solvents include organic solutions comprising an organic diluent, at least one phosphine oxide and at least one proton donating agent, as disclosed in WO 2013/065050 A1 .
  • the solvent used in step I) comprises benzoyltrifluoroacetone (HBTA) and tri-n-octylphosphine oxide (TOPO). In some embodiments, the solvent used in step I) comprises thenoyltrifluoroacetone (TTA) and tri-n-octylphosphine oxide (TOPO). In some embodiments, the solvent used in step I) is a solution of 27 vol% Cyanex® 936P in in dearomatized hydrocarbon fluid (EscaidTM 110).
  • the process further comprises m) adjusting the pH of the acidic aqueous solution comprising manganese cations and impurity cations obtained in step f) to be in the range of from 6.8 to 8.5, for instance, from 7.3 to 8, and precipitating manganese carbonate and/or manganese hydroxide from the solution, n) removing solids from the mixture obtained in step m), o) optionally, adjusting the pH of the solution obtained in step n) to be in the range of from 10 to 12.5, and precipitating metal hydroxides from the solution, and p) optionally, removing solids from the mixture obtained in step o).
  • the process further comprises q) crystalizing cobalt sulfate from the acidic aqueous solution comprising cobalt cations obtained in step g).
  • the process further comprises r) crystalizing lithium sulfate from the acidic aqueous solution comprising lithium cations obtained in step I).
  • the present disclosure also provides a production plant suitable for performing the process of the present disclosure.
  • the production plant comprises a first solvent extraction (SX) unit configured to receive an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations.
  • the first SX unit comprises an extraction module and a scrubbing and stripping module.
  • an aqueous solution is extracted with an organic solvent, an aqueous phase and an organic phase being formed in the process.
  • the organic phase is separated from the aqueous phase and transferred to the scrubbing and stripping module, where it is extracted with an aqueous acid. After scrubbing and stripping, the organic phase is cycled back to the extraction module.
  • Suitable solvent extraction (SX) units are known in the art.
  • the production plant comprises at least one first continuous stirred-tank reactor (CSTR) configured to receive an aqueous effluent of the extraction module of the first SX unit, if a first SX unit is present, or, in the alternative, to receive an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations. If a first SX unit is present, the first CSTR is located downstream of the first SX unit.
  • the at least one first CSTR comprises a dosing device for liquids, heating/cooling means, and gas injection means.
  • Suitable continuous stirred- tank reactors are known in the art.
  • the production plant further comprises at least one first solid/liquid separation device configured to receive an effluent of the first CSTR.
  • the at least one first solid/liquid separation device thus is located downstream of the first CSTR.
  • the first solid/liquid separation device comprises a filter press.
  • the production plant also comprises at least one second continuous stirred-tank reactor (CSTR) configured to receive an aqueous effluent of the at least one first solid/liquid separation device.
  • the second CSTR thus is located downstream of the first solid/liquid separation device.
  • the first CSTR comprises a dosing device for liquids and heating/cooling means. Suitable continuous stirred-tank reactors are known in the art.
  • the production plant further comprises at least one second solid/liquid separation device configured to receive an effluent of the second CSTR.
  • the at least one second solid/liquid separation device thus is located downstream of the second CSTR.
  • the first solid/liquid separation device comprises a filter press.
  • the production plant further comprises a second solvent extraction (SX) unit configured to receive an aqueous effluent of the at least one second solid/liquid separation device.
  • the second SX unit comprises an extraction module and a scrubbing and stripping module.
  • an aqueous solution is extracted with an organic solvent, an aqueous phase and an organic phase being formed in the process.
  • the organic phase is separated from the aqueous phase and transferred to the scrubbing and stripping module, where it is extracted with an aqueous acid. After scrubbing and stripping, the organic phase is cycled back to the extraction module.
  • Suitable solvent extraction (SX) units are known in the art.
  • the production plant further comprises a third solvent extraction (SX) unit configured to receive an aqueous effluent of the extraction module of the second SX unit.
  • the third SX unit comprises an extraction module and a scrubbing and stripping module.
  • an aqueous solution is extracted with an organic solvent, an aqueous phase and an organic phase being formed in the process.
  • the organic phase is separated from the aqueous phase and transferred to the scrubbing and stripping module, where it is extracted with an aqueous acid. After scrubbing and stripping, the organic phase is cycled back to the extraction module.
  • Suitable solvent extraction (SX) units are known in the art.
  • the production plant further comprises a first crystallizer configured to receive an aqueous effluent of the scrubbing and stripping module of the third SX unit and to produce crystals of a first metal salt.
  • a first crystallizer configured to receive an aqueous effluent of the scrubbing and stripping module of the third SX unit and to produce crystals of a first metal salt.
  • Suitable crystallizers are known in the art.
  • the production plant also comprises at least one third continuously stirred tank reactor (CSTR) configured to receive an aqueous effluent of the extraction module of the third SX unit.
  • CSTR continuously stirred tank reactor
  • the third CSTR thus is located downstream of the third SX unit.
  • the third CSTR comprises a dosing device for liquids and heating/cooling means. Suitable continuously stirred tank reactors are known in the art.
  • the production plant further comprises at least one third solid/liquid separation device configured to receive an effluent of the third CSTR.
  • the at least one third solid/liquid separation device thus is located downstream of the third CSTR.
  • the third solid/liquid separation device comprises a filter press.
  • the production plant further comprises a fourth solvent extraction (SX) unit configured to receive an aqueous effluent of the third solid/liquid separation device.
  • the fourth SX unit comprises an extraction module and a scrubbing and stripping module.
  • an aqueous solution is extracted with an organic solvent, an aqueous phase and an organic phase being formed in the process.
  • the organic phase is separated from the aqueous phase and transferred to the scrubbing and stripping module, where it is extracted with an aqueous acid. After scrubbing and stripping, the organic phase is cycled back to the extraction module.
  • Suitable solvent extraction (SX) units are known in the art.
  • the production plant further comprises a second crystallizer configured to receive an aqueous effluent of the scrubbing and stripping module of the fourth SX unit and to produce crystals of a third metal salt.
  • Suitable crystallizers are known in the art.
  • the production plant further comprises at least one fourth continuously stirred tank reactor (CSTR) configured to receive an aqueous effluent of the scrubbing and stripping module of the second SX unit.
  • the fourth CSTR thus is located downstream of the second SX unit.
  • the fourth CSTR comprises dosing devices for liquids and heating/cooling means. Suitable continuously stirred tank reactors are known in the art.
  • the production plant further comprises at least one fourth solid/liquid separation device configured to receive an effluent of the fourth CSTR.
  • the at least one fourth solid/liquid separation device thus is located downstream of the fourth CSTR.
  • the fourth solid/liquid separation device comprises a filter press.
  • the production plant further comprises at least one fifth continuously stirred tank reactor (CSTR) configured to receive an aqueous effluent of the fourth solid/liquid separation device.
  • the fifth CSTR thus is located downstream of the fourth solid/liquid separation device.
  • the fifth CSTR comprises a dosing device for liquids, and heating/cooling means. Suitable continuously stirred tank reactors are known in the art.
  • the production plant further comprises at least one fifth solid/liquid separation device configured to receive an effluent of the fifth CSTR.
  • the at least one fifth solid/liquid separation device thus is located downstream of the fifth CSTR.
  • the fifth solid/liquid separation device comprises a filter press.
  • the first solid/liquid separation device, the second solid/liquid separation device, the third solid/liquid separation device, the fourth solid/liquid separation device, and the fifth solid/liquid separation device each comprise a filter press.
  • FIG. 1 A schematic diagram of an exemplary production plant of the present disclosure is shown in Fig. 1 .
  • the production plant comprises a first solvent extraction (SX) unit 10 which is configured to receive an acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations 1000.
  • the first SX unit 10 comprises an extraction module 11 and a scrubbing and stripping module 12.
  • the acidic aqueous solution comprising nickel, cobalt, manganese, and lithium cations entering the first SX unit 10 is extracted with an organic solvent in the extraction module 11 .
  • the extracted aqueous phase leaves the extraction module 11 as an aqueous effluent 1001.
  • the loaded organic phase is transferred to the scrubbing and stripping module 12, where it is scrubbed and stripped of metal cations with sulfuric acid to produce an acidic aqueous solution comprising the metal cations from the organic phase.
  • the organic phase is recycled to the extraction module 11 , and the acidic aqueous solution comprising the metal cations from the organic phase leaves the scrubbing and stripping module 12 as an aqueous effluent 1002.
  • the production plant further comprises at least one first continuously stirred tank reactor (CSTR) 50 which is configured to receive an aqueous effluent 1001 of the extraction module 11 of the first SX unit 10.
  • the CSTR 50 comprises a dosing device for liquids, heating/cooling means, and gas injection means.
  • a solution comprising sodium carbonate is added to precipitate impurities from the solution.
  • the impurities comprise one or more selected from iron, aluminum, magnesium, calcium, titanium, manganese, residual copper, fluoride, and phosphate.
  • Air is injected into the solution to oxidize any Fe(ll) present to Fe(lll). Iron, aluminum, titanium, and copper precipitate from the solution as hydroxides and/or oxide-hydroxides and/or carbonates, fluorides and/or phosphates,
  • the production plant further comprises at least one first solid/liquid separation device 100 which is configured to receive an effluent 5001 of the first CSTR 50.
  • the precipitated impurities 10002 are removed from the effluent of the first CSTR 50 by solid/liquid separation, e.g., filtration.
  • the production plant further comprises at least one second CSTR 60 which is configured to receive an aqueous effluent 10001 from the first solid/liquid separation device 100.
  • the second CSTR 60 comprises a dosing device for liquids and heating/cooling means.
  • a solution comprising sodium carbonate is added to precipitate residual impurities from the solution.
  • the production plant further comprises at least one second solid/liquid separation device 110 which is configured to receive an effluent 6001 of the second CSTR 60.
  • solids 11002 are recovered from the effluent 6001 of the second CSTR 60 by solid/liquid separation, e.g., filtration.
  • the production plant further comprises a second SX unit 20 which is configured to receive an aqueous effluent 11001 of the at least one second solid/liquid separation device 110.
  • the second SX unit 20 comprises an extraction module 21 and a scrubbing and stripping module 22.
  • the aqueous effluent 12001 of the at least one second solid/liquid separation device 120 is extracted with an organic solvent in the extraction module 21.
  • the extracted aqueous phase leaves the extraction module 21 as an aqueous effluent 2001.
  • the loaded organic phase is transferred to the scrubbing and stripping module 22, where it is scrubbed and stripped of metal cations with sulfuric acid to produce an acidic aqueous solution comprising the metal cations from the organic phase.
  • the organic phase is recycled to the extraction module 21 , and the acidic aqueous solution comprising the metal cations from the organic phase leaves the scrubbing and stripping module 22 as an aqueous effluent 2002.
  • the production plant further comprises a third SX unit 30 which is configured to receive an aqueous effluent 2001 of the extraction module 21 of the second SX unit 20.
  • the third SX unit 30 comprises an extraction module 31 and a scrubbing and stripping module 32.
  • the aqueous effluent 2001 of the extraction module 21 of the second SX unit 20 is extracted with an organic solvent in the extraction module 31.
  • the extracted aqueous phase leaves the extraction module 31 as an aqueous effluent 3001.
  • the loaded organic phase is transferred to the scrubbing and stripping module 32, where it is scrubbed and stripped of metal cations with sulfuric acid to produce an acidic aqueous solution comprising the metal cations from the organic phase.
  • the organic phase is recycled to the extraction module 31 , and the acidic aqueous solution comprising the metal cations from the organic phase leaves the scrubbing and stripping module 32 as an aqueous effluent 3002.
  • the production plant further comprises a first crystallizer 150 configured to receive an aqueous effluent 3002 of the scrubbing and stripping module 32 of the third SX unit 30 and to produce crystals of a first metal salt, e.g., cobalt sulfate.
  • a first metal salt e.g., cobalt sulfate.
  • the production plant further comprises at least one third continuously stirred tank reactor (CSTR) 70 which is configured to receive an aqueous effluent 3001 of the extraction module 31 of the third SX unit 30.
  • the CSTR 70 comprises a dosing device for liquids, and heating/cooling means.
  • water removed from the aqueous effluent 3001 cobalt sulfate and manganese sulfate are added, and subsequently, sodium hydroxide and ammonia are added to precipitate a mixed metal battery material precursor.
  • the production plant further comprises at least one third solid/liquid separation device 120 which is configured to receive an effluent 7001 of the third CSTR 70.
  • a mixed metal battery material precursor 12002 is recovered from the effluent 7001 of the third CSTR 70 by solid/liquid separation, e.g., filtration.
  • the production plant further comprises a forth SX unit 40 which is configured to receive an aqueous effluent 12001 of the at least one third solid/liquid separation device 120.
  • the fourth SX unit 40 comprises an extraction module 41 and a scrubbing and stripping module 42.
  • the aqueous effluent 12001 from the third solid/liquid separation device 120 is extracted with an organic solvent in the extraction module 41 .
  • the extracted aqueous phase leaves the extraction module 41 as an aqueous effluent 4001.
  • the loaded organic phase is transferred to the scrubbing and stripping module 42, where it is scrubbed and stripped of metal cations with sulfuric acid to produce an acidic aqueous solution comprising the metal cations from the organic phase.
  • the organic phase is recycled to the extraction module 41 , and the acidic aqueous solution comprising the metal cations from the organic phase leaves the scrubbing and stripping module 42 as an aqueous effluent 4002.
  • the production plant further comprises a second crystallizer 160 configured to receive an aqueous effluent 4002 of the scrubbing and stripping module 42 of the fourth SX unit 40 and to produce crystals of a second metal salt, e.g., lithium sulfate.
  • a second metal salt e.g., lithium sulfate.
  • the production plant further comprises at least one fourth CSTR 80 which is configured to receive an aqueous effluent 2002 of the scrubbing and stripping module 22 of the second SX unit 20.
  • the fourth CSTR 80 comprises a dosing device for liquids, gas injection means, and heating/cooling means.
  • alkaline solution is added to precipitate manganese carbonate and/or hydroxide.
  • the production plant further comprises at least one fourth solid/liquid separation device 130 which is configured to receive an effluent 8001 of the fourth CSTR 80.
  • at least one fourth solid/liquid separation device 130 manganese carbonate and/or hydroxide 13002 is recovered from the effluent 8001 of the fourth CSTR 80 by solid/liquid separation, e.g., filtration.
  • the production plant further comprises at least one fifth CSTR 90 which is configured to receive an aqueous effluent 13001 of the at least one fourth solid/liquid separation device 130.
  • the fifth CSTR 90 comprises a dosing device for liquids and heating/cooling means.
  • alkaline solution is added to precipitate metal hydroxides.
  • the production plant further comprises at least one fifth solid/liquid separation device 140 which is configured to receive an effluent 9001 of the fifth CSTR 90.
  • metal hydroxides 14002 are recovered from the effluent 9001 of the fifth CSTR 90 by solid/liquid separation, e.g., filtration.
  • Element concentrations in the examples were measured using ICP-OES.
  • An aqueous acid solution obtained from leaching lithium ion battery materials and containing, Ni, Co, Mn, and Li was processed according to the present disclosure, except that sodium hydroxide or sodium carbonate instead of calcium oxide, calcium hydroxide or calcium carbonate was used to adjust the pH in the individual process steps.
  • a solution comprising 27 g/l nickel and 29 g/l sodium was obtained. Water was removed from the solution by evaporation in order to increase nickel concentration in the solution to 96 g/l. However, when nickel concentration reached 51 g/l, precipitation of Na 2 Ni(SO4)2 from the solution occurred.
  • Example 1 was repeated using calcium oxide, calcium hydroxide or calcium carbonate to adjust the pH in the individual process steps. After solvent extraction of cobalt cations, water was removed from the solution by evaporation to increase nickel concentration in the solution to 96 g/l. The concentrated solution contained 37.3 g/l sodium.
  • Table 1 summarizes the composition of the solution of Example 1 before water removal, the hypothetical composition of a concentrate if no precipitation of Na 2 Ni(SO4)2 had occurred, and the composition of the concentrated solution obtained in Example 2.
  • Solution a.1 To the concentrated solution obtained in Example 2, commercially available COSO4 and MnSC (both battery grade) dissolved in deionized water were added to obtain a solution containing Ni, Co, and Mn in a molar ratio of 91 :4.5:4.5. Total transition metal concentration in solution a.1 was 1.45 mol/kg.
  • the compositions of the concentrated solution obtained in Example 2 and solution a.1 are listed in Table 2.
  • Solution y.1 25wt% ammonia in deionized water.
  • the stirrer element was operated at 1100 rpm.
  • Aqueous solution (a.1 ), ([3.1 ) and (y.1 ) were simultaneously introduced into the vessel through the corresponding tubes.
  • the molar ratio of ammonia to transition metal was adjusted to 0.25. Initially, the sum of volume flows was set to adjust the residence time to 10.0 hours.
  • the flow rate of solution ([3.1 ) was adjusted by a pH regulation circuit to keep the pH value in the stirred vessel at a constant value of 12.5 for 1 min of reaction time and thereafter was lowered to 11 .4 for the remaining time of the precipitation reaction.
  • the particle growth was ended by stopping the feed dosing.
  • the slurry obtained was collected and had an average particle diameter (D50) of 3.46 pm and (D90-D10)/D50 of 0.674.
  • a fraction of the slurry was transferred into another 3.2 I stirred tank reactor, which was equipped as described above.
  • the slurry inside the reactor was combined with a solution ([3.1 ) and (y.1 ) at pH-value of 11.4, and an ammonia concentration of 0.5 wt.%.
  • the temperature inside the vessel was set to 55 °C, the stirrer element was operated at 950 rpm and the aqueous solution (a.1 ), ([3.1 ) and (y.1 ) were simultaneously introduced into the vessel through the corresponding tubes and the particles were grown until a particle diameter of 10.6 pm was reached.
  • P-CAM.1 had an average particle diameter (D50) of 10.3 pm, a value of (D90-D10)/D50 of 0.36, a BET surface of 12.6 m 2 /g, and a lithium-content of 200 ppm.
  • the composition of the precursor P-CAM 1 is shown in Table 3.
  • Acidic aqueous solution comprising Ni, Co, Mn, and Li cations
  • Solids Manganese hydroxide and/or carbonate

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Abstract

La présente divulgation concerne un procédé continu et une installation de production pour produire un précurseur de matériau de batterie à base d'hydroxydes métalliques mixtes à partir de charges de recyclage de batterie comprenant des cations nickel, cobalt, manganèse et lithium.
PCT/EP2024/087489 2023-12-19 2024-12-19 Précurseur de matériau de batterie à base d'hydroxydes métalliques mixtes produit à partir de charges de recyclage de batterie Pending WO2025132849A1 (fr)

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KR20110117024A (ko) * 2010-04-20 2011-10-26 한국지질자원연구원 폐배터리의 유가금속 재활용방법
WO2013065050A1 (fr) 2011-11-03 2013-05-10 Bateman Lithium Projetc Ltd Procédés d'élimination d'ions métalliques à partir de solutions aqueuses
CN110422891A (zh) * 2019-08-08 2019-11-08 中国科学院青海盐湖研究所 一种制备镍钴锰三元前驱体的方法、系统及应用
WO2020124130A1 (fr) 2018-12-21 2020-06-25 A.C.N. 630 589 507 Pty Ltd Procédé de recyclage de batteries
CN111455171A (zh) 2019-01-22 2020-07-28 深圳市金航深海矿产开发集团有限公司 一种海底多金属结核提取有价金属并联产锂电正极材料前驱体及掺钛正极材料的方法
WO2023054621A1 (fr) 2021-09-29 2023-04-06 株式会社アサカ理研 Procédé de récupération de métal valorisable à partir d'une batterie lithium-ion usagée
AU2022229686A1 (en) * 2021-03-02 2023-09-21 Pure Battery Technologies Limited Precipitation of metals

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WO2013065050A1 (fr) 2011-11-03 2013-05-10 Bateman Lithium Projetc Ltd Procédés d'élimination d'ions métalliques à partir de solutions aqueuses
WO2020124130A1 (fr) 2018-12-21 2020-06-25 A.C.N. 630 589 507 Pty Ltd Procédé de recyclage de batteries
CN111455171A (zh) 2019-01-22 2020-07-28 深圳市金航深海矿产开发集团有限公司 一种海底多金属结核提取有价金属并联产锂电正极材料前驱体及掺钛正极材料的方法
CN110422891A (zh) * 2019-08-08 2019-11-08 中国科学院青海盐湖研究所 一种制备镍钴锰三元前驱体的方法、系统及应用
AU2022229686A1 (en) * 2021-03-02 2023-09-21 Pure Battery Technologies Limited Precipitation of metals
WO2023054621A1 (fr) 2021-09-29 2023-04-06 株式会社アサカ理研 Procédé de récupération de métal valorisable à partir d'une batterie lithium-ion usagée

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